CN112593107B - Equipment and method for preparing graphene aluminum alloy - Google Patents
Equipment and method for preparing graphene aluminum alloy Download PDFInfo
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- CN112593107B CN112593107B CN202011344695.7A CN202011344695A CN112593107B CN 112593107 B CN112593107 B CN 112593107B CN 202011344695 A CN202011344695 A CN 202011344695A CN 112593107 B CN112593107 B CN 112593107B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
Abstract
The invention discloses equipment and a method for preparing graphene aluminum alloy, and relates to the field of composite materials, wherein the method comprises the following steps: preparing an oleuropein solution, adding pure water into the oleuropein solution until the concentration is 0.1-0.5 mg/ml, adding 0.02-0.05 g of graphene oxide into 400ml of the oleuropein solution with the concentration of 0.1-0.5 mg/ml, adjusting the pH value to 4-6 to obtain a reaction solution, and reacting the reaction solution at the temperature of 50-65 ℃ for 60-70 min to obtain a graphene dispersion solution; and blowing the aluminum alloy powder into the inner tube by using an air heater, wherein the temperature of hot air mixed with the aluminum alloy powder is 60-80 ℃, spraying the hot air through a first nozzle, and simultaneously adding the graphene dispersion liquid into an atomizer for reacting for 45-75 min. The method can reduce the difficulty of mixing the graphene and the aluminum alloy powder, improve the mixing uniformity and promote interface combination.
Description
Technical Field
The invention relates to the field of composite materials, in particular to equipment and a method for preparing graphene aluminum alloy.
Background
The aluminum alloy is one of the most widely applied metal materials at present, and the texture structure and the performance are changed by doping metals such as Mn, Si, Mg, Cu and the like into the metal aluminum, so that the metal structure material with light weight, good electric conduction and heat conduction performance and strong corrosion resistance is obtained, and the metal structure material is widely used in the fields of buildings, daily necessities, aviation and the like.
Because the ductility of the aluminum is good, the doped metal is better improved, but when the aluminum alloy is used as a building material or an aviation material, the building structure needs to have higher bearing and corrosion resistance; the aviation material needs to have excellent ionization radiation resistance, electric conduction, heat conduction and impact resistance, needs to be improved on the existing aluminum alloy, and at present, the aim is achieved mostly by regulating and controlling components, smelting modes and forming processes, but the effect is not ideal.
Therefore, materials such as graphene and carbon nanotubes are added into the aluminum alloy as an additive for compounding, so that the performance of the graphene with high strength and good electric and heat conductivity is introduced into the aluminum alloy, and the corresponding performance is improved.
During preparation, graphene and aluminum alloy powder are uniformly mixed to uniformly disperse the graphene in the aluminum alloy, and the graphene is easy to agglomerate in the aluminum alloy due to the large specific surface area of the graphene and has poor dispersibility.
In order to promote the mixing uniformity of the graphene and the aluminum alloy powder, a ball milling mode is usually adopted for processing at present, but the mode is long in consumed time and complex in process, and in the ball milling process, the interface between the graphene and the aluminum alloy powder is difficult to combine, so that a large amount of energy consumption needs to be consumed in the subsequent preparation process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide equipment and a method for preparing graphene aluminum alloy, which can reduce the difficulty of mixing graphene and aluminum alloy powder and improve the mixing uniformity.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
the equipment for preparing the graphene aluminum alloy comprises a gas guide pipe and a sealed reaction kettle, wherein the gas outlet end of the gas guide pipe is fixed on the inner bottom of the sealed reaction kettle, the gas guide pipe comprises an inner pipe and an outer pipe which are mutually sleeved, a steam fog dispersing space is formed between the inner pipe and the outer pipe and used for conveying atomized graphene dispersion liquid, and the inner pipe is used for conveying aluminum alloy powder mixed with hot air;
the air outlet end comprises a first nozzle and a second nozzle, the second nozzle wraps the outer side of the first nozzle, the first nozzle comprises a fixing plate and a plurality of first steam injection pipes, the first steam injection pipes are obliquely arranged in different directions, the first nozzle is arranged at the air outlet end of the inner pipe, and the air inlet end of the inner pipe is connected with the hot air blower; the second nozzle comprises a plurality of second steam injection holes, and the second steam injection holes are connected with the atomizer through steam transmission pipes.
Furthermore, the inclination angle of the first steam injection pipe is 15-45 degrees.
A method of graphene aluminum alloy, comprising the steps of:
A. preparing an oleuropein solution, adding pure water into the oleuropein solution until the concentration is 0.1-0.5 mg/ml, adding 0.02-0.05 g of graphene oxide into 400ml of the oleuropein solution with the concentration of 0.1-0.5 mg/ml, adjusting the pH value to 4-6 to obtain a reaction solution, and reacting the reaction solution at the temperature of 50-65 ℃ for 60-70 min to obtain a graphene dispersion solution;
B. and blowing the aluminum alloy powder into the inner tube by using an air heater, wherein the temperature of hot air mixed with the aluminum alloy powder is 60-80 ℃, spraying the hot air through a first nozzle, and simultaneously adding the graphene dispersion liquid into an atomizer for reacting for 45-75 min.
Further, the preparation of the oleuropein solution specifically comprises the following steps: according to the mass ratio of 1: 10-15, olive leaves are crushed and then mixed with pure water, the mixture is placed in microwave heating equipment to be heated to 30-50 ℃, then the mixture is placed in an ultrasonic container to be subjected to heat preservation and ultrasonic treatment for 15-25 min, and an oleuropein solution is obtained through filtration.
Furthermore, the concentration of the oleuropein solution is 0.2-0.95 mg/ml.
Further, the following steps are also included between the steps a and B: and adjusting the pH value of the graphene dispersion liquid to 7-8.
Further, the graphene dispersion liquid is characterized by an infrared spectrometer, and compared with graphene oxide, 1720cm corresponding to carboxyl is-1The peak value is obviously reduced, and the hydroxyl group corresponds to 1390cm-1The peak at (a) is also significantly reduced, indicating that the graphene oxide is efficiently reduced.
Further, the C/O ratio of graphene in the graphene dispersion liquid is 7-8.
Further, the ratio of the aluminum alloy powder to the graphene oxide is 1: 100-300 in parts by mass.
Compared with the prior art, the invention has the advantages that:
(1) according to the method for preparing the graphene aluminum alloy, the graphene oxide is reduced through the oleuropein, the C/O ratio of the graphene oxide is improved, the graphene has better dispersity, and additional ball milling or dissolving by adding an organic solvent such as acetone is not needed; meanwhile, the aluminum alloy powder is sprayed to the atomized graphene dispersion liquid, graphene in the atomized liquid can be effectively attached to the surface of aluminum alloy powder particles and covers the aluminum alloy powder particles, the graphene surface in the state can be effectively combined with the interface of the aluminum alloy powder particles, and finally the obtained graphene aluminum alloy particles are good in uniformity and high in quality; the graphene dispersion atomization liquid contains unreacted oleuropein, so that the oxidation-reduction reaction of aluminum alloy powder and water at high temperature can be avoided, and the quality of the graphene aluminum alloy is improved.
(2) According to the equipment for preparing the graphene aluminum alloy, steam fog passes through the steam conveying pipe and then is sprayed out through the second steam spraying hole, and hot air can heat the steam fog dispersing space between the inner pipe and the outer pipe, so that the temperature of a graphene dispersion liquid in the steam conveying pipe is increased, and when the graphene dispersion liquid is sprayed out from the second steam spraying hole, the temperature is higher; simultaneously, first steam jet pipe slope sets up, and steam is to the equidirectional blowout in the sealed reation kettle, can carry out intensive mixing to the reactant in the reation kettle, promotes the effective of reaction to go on.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing a graphene aluminum alloy in an embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view of an outer tube according to an embodiment of the present invention.
In the figure: 1-gas guide tube, 2-sealed reaction kettle, 3-gas outlet end, 4-inner tube, 5-outer tube, 6-first nozzle, 7-second nozzle, 8-first steam injection tube, 9-second steam injection hole and 10-steam transmission tube.
Detailed Description
Embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
Referring to fig. 1 and 2, the invention provides equipment for preparing graphene aluminum alloy, which comprises a gas guide tube 1 and a sealed reaction kettle 2, wherein a gas outlet end 3 of the gas guide tube 1 is fixed on an inner bottom of the sealed reaction kettle 2, the gas guide tube 1 comprises an inner tube 4 and an outer tube 5 which are sleeved with each other, a vapor dispersion space is formed between the inner tube 4 and the outer tube 5 and used for conveying atomized graphene dispersion liquid, and the inner tube 4 is used for conveying aluminum alloy powder mixed with hot air.
The air outlet end 3 comprises a first nozzle 6 and a second nozzle 7, the second nozzle 7 is wound on the outer side of the first nozzle 6, the first nozzle 6 comprises a fixing plate and a plurality of first steam injection pipes 8, the first steam injection pipes 8 are arranged in an inclined mode towards different directions, the inclination angle is 15-45 degrees, the first nozzle 6 is arranged at the air outlet end 3 of the inner pipe 4, and the air inlet end of the inner pipe 4 is connected with a hot air blower; the second nozzle 7 comprises a plurality of second steam injection holes 9, and the second steam injection holes 9 are connected with the atomizer through steam transmission pipes 10.
The embodiment of the invention provides a method for preparing a graphene aluminum alloy, which comprises the following steps:
s1, preparing oleuropein: according to the mass ratio of 1: 10-15, olive leaves are crushed and then mixed with pure water, the mixture is placed in a microwave heating device to be heated to 30-50 ℃, then the mixture is placed in an ultrasonic container to be subjected to heat preservation and ultrasonic treatment for 15-25 min, an oleuropein solution is obtained through filtration, and the concentration of the oleuropein solution obtained through measurement is 0.2-0.95 mg/ml.
S2, preparing a graphene dispersion liquid: adding pure water into the oleuropein solution until the concentration is 0.1-0.5 mg/ml, adding 0.02-0.05 g of graphene oxide into 400ml of the oleuropein solution with the concentration of 0.1-0.5 mg/ml, adjusting the pH value to be 4-6 to obtain a reaction solution, reacting the reaction solution at the temperature of 50-65 ℃ for 60-70 min to obtain a graphene dispersion solution, and adjusting the pH value to be 7-8.
The adjacent hydroxyl groups in the oleuropein can reduce graphene oxide (RO) to obtain RGO, the C/O ratio after reduction is 7-8, and compared with RO, the dispersibility and water solubility are better, so that the dispersibility of RGO in the graphene dispersion liquid is better, meanwhile, the graphene dispersion liquid is characterized by an infrared spectrometer, and compared with graphene oxide, 1720cm corresponding to carboxyl can be obtained-1The peak value is obviously reduced, and the hydroxyl group corresponds to 1390cm-1The peak value is also obviously reduced, and the surface graphene oxide is effectively reduced.
S3, mixing reaction: blowing aluminum alloy powder into the inner tube 4 by using an air heater, wherein the temperature of hot air mixed with the aluminum alloy powder is 60-80 ℃, spraying the hot air through the first nozzle 6, simultaneously adding graphene dispersion liquid into the atomizer, continuously blowing the hot air until the reaction is complete after the aluminum alloy powder is completely blown in, wherein the reaction time is 45-75 min, so as to keep the temperature in the reaction kettle, and simultaneously, enabling the reaction substances to be continuously in a motion mixing state. Wherein the ratio of the aluminum alloy powder to the graphene in terms of graphene oxide is 1: 100-300 in parts by mass.
The steam fog passes through the steam conveying pipe 10 and then is sprayed out through the second steam spraying holes 9, and the hot air heats the steam fog dispersing space between the inner pipe 4 and the outer pipe 5, so that the temperature of the graphene dispersion liquid in the steam conveying pipe 10 rises, and when the graphene dispersion liquid is sprayed out from the second steam spraying holes 9, the temperature is 40-60 ℃.
Simultaneously, the slope of first steam injection pipe 8 sets up, and steam is to the equidirectional blowout in the sealed reation kettle 2, can carry out intensive mixing to the reactant in reation kettle 2, promotes the effective of reaction and goes on.
According to the method, the oleuropein is used for reducing the graphene oxide, so that the C/O ratio of the graphene oxide is improved, the graphene has better dispersibility, and additional ball milling or addition of an organic solvent such as acetone for dissolution is not needed; simultaneously, the aluminium alloy powder sprays the graphite alkene dispersion liquid after to the atomizing, and graphite alkene in the atomizing liquid can effectively adhere to the surface of aluminium alloy powder granule and with its cladding, and the graphite alkene surface under this state can effectively combine with the interface of aluminium alloy powder granule, and the graphite alkene aluminium alloy granule homogeneity that finally obtains is better, and the quality is higher.
The graphene dispersion atomization liquid contains unreacted oleuropein, so that the oxidation-reduction reaction of aluminum alloy powder and water at high temperature can be avoided, and the quality of the graphene aluminum alloy is improved.
The present invention is described in detail below with reference to 3 examples.
Example 1
Preparing oleuropein: according to the mass ratio of 1:10, olive leaves are crushed and then mixed with pure water, the mixture is placed in a microwave heating device to be heated to 30 ℃, then the microwave heating device is placed in an ultrasonic container to carry out heat preservation and ultrasonic treatment for 15min, an oleuropein solution is obtained through filtration, and the concentration of the oleuropein solution obtained through measurement is 0.12 mg/ml.
Preparing a graphene dispersion liquid: adding pure water into the oleuropein solution until the concentration is 0.3mg/ml, adding 0.02g of graphene oxide into 400ml of the oleuropein solution with the concentration of 0.3mg/ml, adjusting the pH value to be 6 to obtain a reaction solution, placing the reaction solution at the temperature of 60 ℃ for reacting for 60min to obtain a graphene dispersion solution, and adjusting the pH value to be 7.
Mixing and reacting: blowing aluminum alloy powder into the inner tube 4 by using an air heater 8, wherein the hot air mixed with the aluminum alloy powder is 60 ℃, and is sprayed out through the first nozzle 6, meanwhile, adding graphene dispersion liquid into the atomizer 8, and continuously blowing hot air until the reaction is complete after the aluminum alloy powder is completely blown in, wherein the reaction time is 75min, so as to keep the temperature in the reaction kettle, and simultaneously, enabling the reaction substance to be continuously in a motion mixing state. In this example, 1kg of graphene oxide and 200kg of aluminum alloy powder were used.
Example 2
Preparing oleuropein: according to the mass ratio of 1:10, olive leaves are crushed and then mixed with pure water, the mixture is placed in a microwave heating device to be heated to 30 ℃, then the microwave heating device is placed in an ultrasonic container to carry out heat preservation and ultrasonic treatment for 25min, an oleuropein solution is obtained through filtration, and the concentration of the oleuropein solution obtained through measurement is 0.95 mg/ml.
Preparing a graphene dispersion liquid: adding pure water into the oleuropein solution until the concentration is 0.5mg/ml, adding 0.05g of graphene oxide into 400ml of the oleuropein solution with the concentration of 0.5mg/ml, adjusting the pH value to be 6 to obtain a reaction solution, placing the reaction solution at the temperature of 65 ℃ for reacting for 70min to obtain a graphene dispersion solution, and adjusting the pH value to be 8.
Mixing and reacting: blowing aluminum alloy powder into the inner tube 4 by using an air heater, wherein the temperature of hot air mixed with the aluminum alloy powder is 80 ℃, the hot air is sprayed out through the first nozzle 6, meanwhile, the graphene dispersion liquid is added into the atomizer, after the aluminum alloy powder is completely blown in, the hot air is continuously blown in until the reaction is complete, the reaction time is 45min, so that the temperature in the reaction kettle is kept, and meanwhile, the reaction substances are continuously in a motion mixing state.
In this example, 0.5kg of graphene oxide and 150kg of aluminum alloy powder were used.
Example 3
Preparing oleuropein: according to the mass ratio of 1:15, olive leaves are crushed and then mixed with pure water, the mixture is placed in a microwave heating device to be heated to 40 ℃, then the microwave heating device is placed in an ultrasonic container to carry out heat preservation and ultrasonic treatment for 20min, an oleuropein solution is obtained through filtration, and the concentration of the oleuropein solution obtained through measurement is 0.6 mg/ml.
Preparing a graphene dispersion liquid: adding pure water into the oleuropein solution until the concentration is 0.13mg/ml, adding 0.04g of graphene oxide into 400ml of the oleuropein solution with the concentration of 0.3mg/ml, adjusting the pH value to be 5 to obtain a reaction solution, placing the reaction solution at the temperature of 60 ℃ for reacting for 65min to obtain a graphene dispersion solution, and adjusting the pH value to be 7.
Mixing and reacting: blowing aluminum alloy powder into the inner tube 4 by using an air heater, wherein the temperature of hot air mixed with the aluminum alloy powder is 75 ℃, spraying the hot air through the first nozzle 6, simultaneously adding graphene dispersion liquid into the atomizer, continuously blowing the hot air until the reaction is complete after the aluminum alloy powder is completely blown in, and keeping the temperature in the reaction kettle for 65min, and simultaneously enabling the reaction substances to be continuously in a motion mixing state. In this example, 1kg of graphene oxide and 100kg of aluminum alloy powder were used.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone with the teaching of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as the present invention, are within the protection scope.
Claims (7)
1. The utility model provides an equipment of preparation graphite alkene aluminum alloy, includes air duct (1) and sealed reation kettle (2), its characterized in that: the air outlet end (3) of the air guide tube (1) is fixed on the inner bottom of the sealed reaction kettle (2), the air guide tube (1) comprises an inner tube (4) and an outer tube (5) which are mutually sleeved, a vapor dispersion space is formed between the inner tube (4) and the outer tube (5) and used for conveying atomized graphene dispersion liquid, and the inner tube (4) is used for conveying aluminum alloy powder mixed with hot air; the air outlet end (3) comprises a first nozzle (6) and a second nozzle (7), the second nozzle (7) is wound on the outer side of the first nozzle (6), the first nozzle (6) comprises a fixing plate and a plurality of first steam injection pipes (8), the first steam injection pipes (8) are obliquely arranged in different directions, the first nozzle (6) is arranged at the air outlet end (3) of the inner pipe (4), and the air inlet end of the inner pipe (4) is connected with a hot air blower; the second nozzle (7) comprises a plurality of second steam injection holes (9), the second steam injection holes (9) are connected with the atomizer through steam transmission pipes (10), and the inclination angle of the first steam injection pipe (8) is 15-45 degrees.
2. A graphene aluminum alloy preparation method based on the graphene aluminum alloy preparation apparatus of claim 1, characterized in that: the method comprises the following steps: A. preparing an oleuropein solution, adding pure water into the oleuropein solution until the concentration is 0.1-0.5 mg/ml, adding 0.02-0.05 g of graphene oxide into 400ml of the oleuropein solution with the concentration of 0.1-0.5 mg/ml, adjusting the pH value to 4-6 to obtain a reaction solution, and reacting the reaction solution at the temperature of 50-65 ℃ for 60-70 min to obtain a graphene dispersion solution; B. and blowing the aluminum alloy powder into the inner pipe (4) by using an air heater, wherein the temperature of hot air mixed with the aluminum alloy powder is 60-80 ℃, spraying the hot air through the first nozzle (6), and simultaneously adding the graphene dispersion liquid into an atomizer for reacting for 45-75 min.
3. The method of claim 2, wherein: the preparation method of the oleuropein solution specifically comprises the following steps: according to the mass ratio of 1: 10-15, olive leaves are crushed and then mixed with pure water, the mixture is placed in microwave heating equipment to be heated to 30-50 ℃, then the mixture is placed in an ultrasonic container to be subjected to heat preservation and ultrasonic treatment for 15-25 min, and an oleuropein solution is obtained through filtration.
4. The method of claim 3, wherein: the concentration of the oleuropein solution is 0.2-0.95 mg/ml.
5. The method for preparing the graphene aluminum alloy according to claim 4, wherein: the method also comprises the following steps between the steps A and B: and adjusting the pH value of the graphene dispersion liquid to 7-8.
6. The method of claim 5, wherein: the C/O ratio of graphene in the graphene dispersion liquid is 7-8.
7. The method of claim 6, wherein: the ratio of the aluminum alloy powder to the graphene oxide is 1: 100-300 in parts by mass.
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| GB9302387D0 (en) * | 1993-02-06 | 1993-03-24 | Osprey Metals Ltd | Production of powder |
| GB2393452B (en) * | 2002-08-28 | 2005-12-28 | C A Technology Ltd | Improvements to powder production and spraying |
| WO2010102655A2 (en) * | 2009-02-16 | 2010-09-16 | Bayer International Sa | A compound material comprising a metal and nano particles and a method for producing the same |
| CN201524627U (en) * | 2009-11-04 | 2010-07-14 | 清华大学 | Spray gun nozzle for intersection-converge spraying outside the spray gun |
| CN103072981B (en) * | 2013-02-26 | 2014-12-17 | 武汉大学 | Preparation method for graphene |
| CN205218054U (en) * | 2015-11-10 | 2016-05-11 | 常州二维碳素科技股份有限公司 | Ultrasonic atomization mixing apparatus |
| US10850496B2 (en) * | 2016-02-09 | 2020-12-01 | Global Graphene Group, Inc. | Chemical-free production of graphene-reinforced inorganic matrix composites |
| CN206372992U (en) * | 2016-12-08 | 2017-08-04 | 广东伟业铝厂集团有限公司 | A kind of paint finishing |
| CN206262384U (en) * | 2016-12-13 | 2017-06-20 | 长兴创智科技有限公司 | A kind of discontinuity medicinal powder sprays mixing arrangement |
| CN107671301A (en) * | 2017-10-27 | 2018-02-09 | 成都视必康医疗科技有限公司 | A kind of graphene Cu-base powder preparation facilities |
| CN107598179A (en) * | 2017-10-27 | 2018-01-19 | 成都格莱飞科技股份有限公司 | The flusher that a kind of graphene Cu-base powder makes |
| CN208853701U (en) * | 2018-08-24 | 2019-05-14 | 新疆烯金石墨烯科技有限公司 | A kind of preparation facilities of graphene aluminium alloy powder |
| CN210208659U (en) * | 2019-07-10 | 2020-03-31 | 河北烯创科技有限公司 | Graphite alkene metal powder processingequipment |
| CN211840125U (en) * | 2019-12-31 | 2020-11-03 | 江苏变色龙微粉技术有限公司 | Metal powder coating cladding equipment |
| CN111014659A (en) * | 2019-12-31 | 2020-04-17 | 江苏变色龙微粉技术有限公司 | Metal powder coating cladding and binding device and working method thereof |
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Address after: Room 205, 2nd Floor, Building 1, No. 355, Binhai Twelve Branch Road, Xinghai Street, Wenzhou Economic and Technological Development Zone, Wenzhou City, Zhejiang Province, 325000 Patentee after: Zhejiang xiangshixin Technology Co.,Ltd. Address before: 325000 2nd floor, building 1, No. 355 Binhai 12th Branch Road, Xinghai street, Wenzhou Economic and Technological Development Zone, Wenzhou City, Zhejiang Province Patentee before: Zhejiang xiangshixin Technology Co.,Ltd. |
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| CP02 | Change in the address of a patent holder |